CN102639438B - For the production of reactor and the method for silicon - Google Patents

For the production of reactor and the method for silicon Download PDF

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Publication number
CN102639438B
CN102639438B CN201080053022.4A CN201080053022A CN102639438B CN 102639438 B CN102639438 B CN 102639438B CN 201080053022 A CN201080053022 A CN 201080053022A CN 102639438 B CN102639438 B CN 102639438B
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reactor
silicon
described reactor
wall
gas
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CN102639438A (en
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约瑟夫·菲尔特维特
沃纳·O·菲尔特维特
阿韦·霍尔特
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DYNATEC ENGINEERING AS
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DYNATEC ENGINEERING AS
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    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number
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    • B01J19/28—Moving reactors, e.g. rotary drums
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
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    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
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    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/08—Reaction chambers; Selection of materials therefor
    • C—CHEMISTRY; METALLURGY
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
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Abstract

For the production of the reactor of silicon, this reactor comprises reactor volume part, this reactor is unique, because this reactor comprises or is operationally arranged into for the siliceous reactant gases of chemical vapour deposition (CVD) being arranged at least one device rotated in reactor volume part.For the production of the method for silicon.

Description

For the production of reactor and the method for silicon
Technical field
The present invention relates to the silicon produced for solar cell and electron device.More specifically, the present invention relates to the purposes of reactor for the production of silicon and method and this reactor.
Background of invention and prior art
In order to meet future source of energy demand, the new technology of the reproducible uncontamination energy must be developed.In this context, sun power is one of most interested energy.
Silicon is starting material crucial in electronic industry and solar industry.Although for embody rule, there is alternative material, polysilicon and silicon single crystal will be in a foreseeable future preferred materials.The availability improved when producing polysilicon and the economy of improvement are using the development opportunity improved in electronic industry and solar industry and strengthen the purposes of sun power as renewable energy source.
In order to produce enough purity for the silicon in sun power or electron device, generally use chemical gaseous phase depositing process now.For CVD, the Siemens process of different editions is for the production of the most general method of polysilicon.By in silicon-containing gas such as silane or trichlorosilane or other gas such as hydrogen or argon gas feed to container and siliceous deposits on resistive heating rod.Energy requirement and demand for labour high.At patent disclosure US3,979, give the more detailed description of this technique in 490.Current CVD reactor and especially a problem of Siemens reactor be that they only utilize the partial reaction gas be fed in reactor.Major part gas is directly by reactor and as part dissipation from reactor of residual gas.The generation of this problem is due to the fact that it is only the reactant gases that gas diffusion drives in reactor.This causes slow gas flow and most of reactant gases never arrived reaction surface before reactor dissipation.In order to avoid wasting the silicon-containing gas do not utilized, need the waste gas from CVD reactor is stood comprehensively and the cleaning course of costliness.
The less method generally used of the another kind of CVD is fluidized-bed, and wherein silicon seed particle is surrounded by the air-flow risen and is maintained in the air-flow of rising, because air-flow comprises silicon-containing gas, so silicon can be deposited in seed particles from silicon-containing gas.Use the advantage of this fluidized-bed to be the huge surface-area that silicon can deposit on it, this realizes strengthening ground and manufacturing feasibility and lower energy consumption continuously.But, be in fact difficult to obtain and will grow into the practicality of enough large particle taking-up and simple method.Or rather, be difficult to the granular size in control flow check fluidized bed reactor, and be very difficult to the distribution of the particle in the reactor of red-tape operati.The uneven distribution of particle affects flow state, and this affects again the deposition of temperature distribution and silicon.The method needs from reactor, add new particle or form little particle in the reactor during operation.Discharging the large particle in reactor bottom and adding size needs to control many parameters by the little particle increased simultaneously, and proved along with time lapse, this is very difficult in actually operating.The common problem of fluidized-bed reactor is that particle grows together and stops fluidisation and silicon to deposit on the internal surface of reactor and nozzle undesirably gradually, this makes nozzle and reactor volume part (reactorvolume) blocking, thus stops producing.Walk on patent disclosure US4.818.495 the 2nd hurdle the 40th in the 3rd hurdle the 20th row and discuss this problem in patent disclosure US5.810.934.These patents further comprises to have fluidized-bed and auxiliary equipment CVD method and comprise gaseous mixture, depositing temperature production silicon operating parameters and problem and be limited in interior elaborating.
The common problem of current CVD reactor is that little silica dust grain (being called fine powder (fine)) is formed at inside reactor.If this problem occurs when gas reaches decomposition temperature before close to reaction surface, when little gas swirl is formed, gas can be there is before close to reaction surface, reach decomposition temperature.These little silicon grains not to deposit on reaction surface by residual gas from reactor dissipation.Along with the time, fine powder forms the silicon of significant quantity, the silicon of this significant quantity only to a certain extent time be just utilized.Need the demand of the selectable technology favourable relative to the one or more problems in the problems referred to above.
Described demand is met: in the patent of the open NO20092111 of patent on May 29th, 2009, apply DynatecEngineering by following invention part.Described invention provides produces the reactor of silicon by chemical vapour deposition, this reactor comprise form container reactor body, at least one entrance for silicon-containing gas, at least one outlet and as reactor a part or be operationally arranged at least one heating installation of reactor.This reactor is unique, because namely at least one major portion silicon manufacture of reactor body is made up of silicon, this part is exposed to chemical gas phase and is heated in described deposited on portions silicon.
The basic thought of above-mentioned reactor is exposed to all parts of silicon-containing gas or the material of integral part by advantageously having highly purified silicon or being made up of other non-polluting material, silicon deposited wittingly and can be controlled so as to occur on described material.Avoid or reduce and be separated relevant known problem and the various problems relevant with blocking with making silicon with other materials.Meanwhile, how existence can build the many other possibility with operant response device (comprise and can how to realize heating).But, both do not describe in NO20092111 or any concrete orientation of Indicator Reaction device entrance, and do not described yet or indicate any concrete flow pattern except fluidized-bed, and therefore the object of the invention is to improve the reactor for the production of silicon and method further.
Summary of the invention
Described object is met by the present invention, the invention provides a kind of reactor producing silicon, this reactor comprises reactor volume part, this reactor is unique, because this reactor comprises or is operationally arranged into for the siliceous reactant gases of chemical vapour deposition (CVD) being arranged at least one device rotated in reactor volume part.
For the siliceous reactant gases of chemical vapour deposition (CVD) is arranged in the electric motor that the device rotated in reactor volume part is preferably rotatable reactor.Additionally or selectively, special entrance can be adopted to arrange, such as, some entrances on the end plate rotated with reactor, the entrance of inclination and spinner member.Preferably, reactor by around main axis symmetrical rotary, such as, has vertical tube or the level pipe of circular cross section, to realize uniform flow pattern together with internal surface.Reactor can be the one in two main embodiment (namely vertical irrotational reactor and rotatable reactor).In non-rotating reactor, obtain tangential speed component and in reactor volume part, realize the mode of spiral path to make gas, the entrance, blade and/or the spinner member that make gas pass through to tilt rotate.In rotatable reactor, electric motor or equivalent are used for rotatable reactor, but entrance can be fixing, or it can rotate with reactor, and entrance can be arranged tiltably possibly or have spinner member.
Most preferred embodiment is normally without seed particles or fluidized-bed but comprise the rotatable reactor of entrance rotated with reactor; wherein thus more parallel streamline can be obtained; this produces particularly advantageous result, because this makes the formation of silica dust grain (fine powder) minimum.Rotate and produce such flow pattern, it causes at reactor wall, or the siliceous reactant gases of very high density is produced or rather at the sidewall of described reactor, and the deposition of silicon can be controlled in such mode intentionally as occurring on the reactor wall, and described mode makes reactor tight by the silicon growth deposited more or less.After making reactor rotate certain hour, the inwall of most of siliceous reactant gases orientating reaction device thus will be high density, and described gas and wall are by make disturbance flow with gas separation effect and therefore to disturb the mode of the minimize turbulence of the deposition of silicon to rotate under identical speed.Unexpectedly, confirm that more parallel streamline or flow pattern have more advantages than other flow patterns.
Reactant gases comprises silicon-containing gas usually, is advantageously the silane mixed with hydrogen.After silane decomposes and silicon release, hydrogen also forms residual product.In some cases, reactant gases also containing little silicon grain, can be called fine powder.Principle of the present invention is difference large between the quality of silicon-containing gas and the quality of hydrogen, and usually, silane weight is about 16 times of hydrogen weight.According to Newton's second law, power equals quality and is multiplied by acceleration, and when reactant gases is configured to rotate, heavy siliceous molecule is exposed to larger power by than light hydrogen molecule.Rotate and produce centripetal acceleration or centrifugal effect, this causes very effective separating effect and the heavy silicon-containing gas reactor wall moving generation deposition on it pushed outwards.Reactor is suitable for the controlled filling of silicon deposited, and therefore, at least one major portion silicon manufacture of reactor, is namely made up of silicon, or comprises the coated inside of silicon, the circular cylinder shape sidewall of such as metallurgical grade or CVD silicon or EFG silicone tube or analogue.More properly, reactor is operationally arranged at least one heating installation, at least one heating installation described wittingly reacting by heating wall at least partially or whole reactor wall, silicon is deposited on wall wittingly by CVD, thus with deposition silicon complete filling reactor volume part.By this way, the whole reactor that the silicon be deposited is filled completely or sidewall of reactor can be used as solar cell or electronic silicon.But, there are other wall materials in addition to silicon and wall is wholly or partly the reactor heated wittingly is also applicatory and is embodiments of the present invention, therefore technique effect of the present invention be still shockingly good, especially for rotatable reactor.Reactor tube with other materials manufacture in addition to silicon or can be made up of other materials in addition to silicon, the silica quartz pipe of the reasonable price that such as can be removed entirely after reactor process.The fusing of the silicon of deposition can be made to leave without silicon wall or the reactor only with EFG silicon coating by induction melting or by another kind of heating installation (such as suitable stove), optionally, the wall elements of pollution can be machined or cut away.
Reactor is advantageously formed as the right cylinder with circular interior cross-section being arranged to upright or level; electric motor for rotatable reactor is preferably operationally arranged into reactor; the outlet of poor silicon gas is coaxially arranged cylinder axis at least one end; at least one heating installation is operationally arranged in the outside or inside of reactor, have or inert-free gas and/or cooling gas protection.Reactor advantageously comprises at least one end plate rotated with reactor, and this end plate is equipped with one or more entrances of siliceous reactant gases.One or more entrance is arranged on rotation and/or is arranged to the distance different apart from rotation, and end plate such as can be arranged into the Supply House of reactant gases hermetically and rotatably, and as an example, end plate is the rotatable top on this room.Selectively, Supply House can rotate with reactor, and this makes end plate be the spaced walls with nozzle between Supply House and reactor volume part.Outlet can correspondingly by preferred arrangements.End plate is preferably made by having the material lower than the thermal conductivity of the rest part of reactor, such as or selectively comprises the composite Materials Design of the material with different thermal conductivity, to maintain the temperature of reaction of reactor wall better.
In alternate embodiments, reactor is formed as the vertical vertical cylinder with circle or substantial circular cross section, sidewall high-quality metallurgical grade or purer silicon manufacture, and one or more entrance is arranged tiltably in bottom to make to be ejected into silicon-containing gas in reactor in the mode of advancing along the outlet on wall spiral path orientating reaction device top upwards, and wherein the orientation of entrance and gas comprises the durection component of the durection component being parallel to cylinder axis and the circumference being parallel to inner cylinder body wall.Reactor advantageously comprises or is operationally provided with the heating installation on reactor outside.Heating installation is advantageously shaped as the wreath (helix) of the spiral path that the jet flow stream be parallel in reactor is advanced along it.
Present invention also offers a kind of method of being produced silicon in reactor according to the present invention by vapour deposition and/or clean silicon-containing gas, the method is unique, the method is to be arranged in by the siliceous reactant gases of chemical vapour deposition (CVD) in reactor volume part and rotates, this is by operation at least one device for realizing this rotation, preferably uses one or more reactors that are arranged side by side and/or series connection.This means when by while operating reactor carry out depositing silicon under typical CVD operating parameters, preferably by means of the device of the ingress at reactant gases or layout and/or the electric motor by rotatable reactor, by siliceous reactant gases, preferably all siliceous reactant gasess are arranged to rotate at least partially.The operation of reactor is batchwise process or is first successive processes and is batchwise process after a while.
With make the large bulk-growth of the cross section of reactor closely mode preferably by chemical vapour deposition, silicon is deposited on the reactor wall wittingly, therefore the contents of reactor or the contents of reactor and reactor wall can be used on for the production of the other stage in the technique of the silicon of solar cell and/or electron device object.Best, reactor is rotated by electric motor, due to previous reasons, possibly, injected current to make silicon-containing gas with the inwall along reactor, preferably along the total length of reactor or the spiral path mode of advancing of height directed.
Present invention also offers the purposes of reactor according to the present invention for the production of the siliceous reactant gases of silicon and/or the clean CVD reactor supply from other reactors according to the present invention or other types, or gas is originated from other.
The present invention is based on and build further according to the invention of NO20092111, NO20092111 has such reactor: in the reactor, be exposed to the material manufacture of all parts of silicon-containing gas or quite most material non-polluting material, preferably high quality silicon/be made up of non-polluting material, the preferably material of high quality silicon, the deposition of silicon can be controlled to wittingly and occur on described material.The present invention is unique, because by rotating whole reactor or partial reaction device, and/or by the acclivitous hole in base plate or use spinner member, described gas is supplied in reactor, by siliceous reactant gases, the medullary ray be arranged to around reactor rotates.When adopting acclivitous hole, to make the acquisition of described gas along the path of reactor wall, the mode of preferred spiral path, is supplied to reactant gases in reactor.Therefore, to make gas along the mode that wall rotates in reactor, gas obtains the velocity component being tangential to reactor wall.Meanwhile, vertical speed rate component will order about reactant gases along wall upwards.
When adopting acclivitous hole; in the simplest form of reactor; reactor formation has encloses container that is cylindrical or polygonal shape; this encloses container is substantially with silicon or other non-polluting material manufactures/be made up of silicon or other non-polluting material, and silicon or other non-polluting material are for chemical vapour deposition on inside under without silicon seed particle or fluidized-bed.The mode of the velocity component being tangential to wall and velocity component is upwards obtained in the reactor, with the angle tilted relative to sea line injection air-flow to make air-flow.To make air-flow along the wall flowing of reactor and to realize the mode that rotates around the medullary ray of reactor, air-flow is supplied in reactor.Reactor is configurable in heating chamber, but, except in heating chamber or replace in heating chamber, heating installation is operationally arranged in the reactor, be arranged on reactor or be arranged in reactor outside.Maintain to make reactant gases and rotate, reactor is heated preferably by heating unit, and heating unit is outside at reactor, follow spiral path around reactor.Thus, heating can be controlled by this way: be initially deposited on to make silicon and deposit in inside near the mode in those parts of the wall of heating unit.Therefore, deposition will form spiral path, and spiral path will contribute to gas and keep it to rotate up in the reactor.Deposition will continue along whole wall, and deposition region will increase gradually due to the helical surface of wall.Deposition occurs, until wall has grown into enough closely thus can not or this technique of infeasible continuation economically.Be that, compared with the gas directly to upper flowing, air-flow is by longer distance of advancing along wall with the advantage of spiral path supply air-flow.This is favourable, because gas contacts with the more large regions that can occur thereon to deposit, and the top of air-flow from the bottom of reactor to reactor will spend more times.This causes the possibility depositing/discharge more silicon in gas, thus improves gas effciency.
Arrange that the alternative way of entrance as the aforementioned is arranged on entrance by spinner member, such as, spinner member is arranged on central inlet.Being arranged in such a way entrance is preferred embodiment, because can not need to carry out under too many effort changing different entrances.Spinner member or screw-in element can be implemented in a number of different ways by trapped orbit and/or rotor, and think well known in the art, and will be not described further herein.
The large advantage of gas rotating is made to be that supposition produces the centripetal force be separated by reactant gases.In order to deposit, enough siliceous reactant gasess must be there is by near the silicon wall that heats.After deposition occurs, the residual gas (being also called poor silicon residual gas) of poor silicon is the gas near silicon wall.In order to there is further deposition, new silicon-containing gas is in order to pass poor silicon gas with wall contact need.Silicon-containing gas, is also called Silicon-rich reactant gases, than poor silicon residual gas body weight remaining after release and depositing silicon.As an example, silane gas is obviously than hydrogen weight, and hydrogen forms the residual gas after release silicon.Because gas moves upward in the reactor, then because siliceous deposits is on wall, in gas, the concentration of silicon will decline.There is the gas of high content silicon because its weight is by centripetal acceleration the highest for acquisition.Therefore, will concentration gradient be produced in gas, and along reactor wall, there is the highest silicon concentration and towards center, there is minimum silicon concentration.Therefore, produce deposition gas by all the time near occur deposition place, the gas effciency of this sedimentation rate causing time per unit higher and improvement.The residual gas being arranged in the center of orientating reaction device such as by top board hole in the heart from reactor dissipation.
Centripetal acceleration also by affecting the little silica dust grain that may be formed in CVD reactor, is called fine powder.Compare the gas molecule around these particles, these particles are heavy.Therefore, these particles will outwards be ordered about orientating reaction wall, and thus, they form a sedimental part and can be partially recrystallized on wall.Therefore the serious problems relevant with fine powder that existing CVD reactor exists will be reduced in the extreme.
Therefore, reactor of the present invention additionally can be used as the after-treatment system of the silicon CVD reactor of another kind of type.Reactor of the present invention is connected to the outlet of traditional CVD reactor (such as Siemens reactor).The residual gas produced by silicon-containing gas, little silica dust grain (fine powder), reaction and the exit gas that form of possible mixed gas are configured to rotation and separated.The silicon-containing gas do not utilized and fine powder are outwards ordered about orientating reaction wall, and new deposition occurs on the reactor wall.Light gas is left by outlet.Therefore, reactor becomes the cleaning system of the different components of the exit gas being separated current CVD reactor, and it replaces the cleaning system of the costliness adopted at present, and these cleaning system contribute in fact silicon production simultaneously.Therefore, reactor of the present invention can be connected to " waste gas " of any reactor or export or any usual sources, comprises the reactor of the present invention that is linked in sequence.
Metallurgical method can be used at present to produce silicon, produce the silicon of Metallurgical Quality.This makes it possible to reasonable price structure reactor wall or silicone tube.Because the substantial volume of silicon weight in airtight or complete reactor or major portion have the purity higher than metallurgical grade silicon, the whole reactor with high purity silicon contents can be melted with recrystallization, and for electronic industry and/or efficient solar cell, wherein average purity will be enough.Possibly, if only the highest purity is acceptable, then in on-contaminated mode, such as, by the Water Cutting to described layer, mechanical workout or fusing, the external portion of metallurgical grade silicon can be removed.Optionally, reactor can with the identical highly purified silicon manufacture of its production/be made up of the identical highly purified silicon with its production, the quality of this silicon is suitable for electronic industry.Compared with attainable now, dispose airtight or complete reactor simplifiedly quite greatly and cause the less process of silicon and pollution.
Can be selected from known for heating according to the equipment of reactor of the present invention, can the heating installation of operational applications, but, they advantageously comprise relevant or noncoherent incandescence of any applicable wavelength and effect, such as microwave source, radio wave source, visible light source, infrared source and/or ultraviolet source, be preferably infrared source.
Accompanying drawing explanation
Set forth some embodiments of the present invention in the accompanying drawings, wherein:
Fig. 1 has set forth according to the vertical reactor with circle or substantial circular cross section of the present invention;
Fig. 2 has set forth the vertical reactor in outside with spiral type heated equipment;
Fig. 3 has set forth the enforcement of the entrance in bottom vertical reactor; And
Fig. 4 has set forth according to particularly advantageous reactor of the present invention.
Describe in detail
With reference to figure 1, reactor is closed or substantially closed cylindrical or polygonal container, have wall (1), top board (7) and base plate (4), reactor is preferably with metallurgical grade purity or purer silicon manufacture/be made up of metallurgical grade purity or purer silicon.Selectively, reactor is made up of other feasible materials.Polygonal container is assembled by flat plate.Reactor is formed heating unit (3) around the wreath of reactor or helix structure around, heating unit (3) for complete or be divided into several sections.Described heating unit can also be implemented in the mode of short, straight element, inclination, and making them is in general approximate spiral thing.The reactant gases (6) be supplied to by base plate (4) is silicon-containing gas, is preferably SiH 4or SiHCl 3, be as a rule and H 2the silicon-containing gas of gas and vapor permeation.With reference to figure 2 and 3, the base plate (4) of reactor comprises one or more through hole (5), and one or more through hole (5) is as the nozzle of reactant gases (6).To make, when wall inwardly grows the mode that stylish nozzle can come into operation, hole to be arranged in ideally on the line between its center and cylindrical wall.Feasiblely, can around the some nozzles of circumference.With the patten's design nozzle bore (5) making air-flow obtain tangential velocity component (12) and vertical speed rate component.This is implemented, can see from side as shown in Figure 3 because the hole tilted extends through base plate.The angle in hole preferably equals helix angle, the pitch angle of heating unit.Therefore, when air-flow upward vertical movement, advance in the inner side (2) of air-flow by the rotation (14) realized around the medullary ray of reactor and along cylindrical wall.Top board (7) also comprises hole (8), residual gas (9) is by hole (8) dissipation, the resistates that this residual gas (9) is reactant gases (6), forms primarily of H2 in almost desirable process.Hole (8) in top board (7) is disposed in center in the following manner: make poor silicon residual gas (9) can dissipation, but remaining reactant gases (6) can rotate, until silicon as much as possible is released along reactor wall (2).If hole (8) are tubulose and slightly extend downwardly into may to be favourable in reactor.This can produce whirlwind effect, and whirlwind effect can further improve the utilization ratio of reactant gases.With desirable speed, preferably there is parallel streamline, namely in the mode making helical flow extend to reactor head, be there is by hole (5) supply in base plate (4) air-flow of reactant gases (6).Reactant gases (6) enters the bottom of reactor with the inner side (2) that acclivitous angle is tangential on wall.Therefore, the medullary ray along wall (2) flowing and around reactor rotates by gas.Due to the position of heating unit (3) and the different heating of reactor wall, siliceous deposits is to by the wall (2) that heats is upper and settling forms wreath (10) on the inner side (2) of reactor wall.Residual gas (9) will eventually through hole (8) dissipation in top board (7).
Base plate (4) can be equipped with centre hole (11), with the reactant gases allowing vertical injection other (6).This can contribute to the deposition that silicon even more balances in the vertical direction of reactor, if especially true when the flow velocity of helical flow is significantly greater than the flow velocity of vertical injection stream.The central gas a fluid stream of reactant gases will be caught by the reactant gases (14) rotated and be forced to the inner side (2) of outside orientating reaction wall.If vertical deposition controlled by the cross section of centre hole (11) and air flow stream by centre hole (11) upwards, be then favourable.
In polygonal container, base plate additionally can be equipped with upright opening (15), and upright opening (15) is positioned at the every nook and cranny place in the transitional region between two sidewalls.When starting reactor by uprush supply passing hole (15) for some time of reactant gases will be had, silicon can fast deposition between the sidewalls, thus sealed reactor.Realize the leakage limiting silicon-containing gas very early thus, cause sealing connection gradually owing to revealing, make polygonal container obtain more circular internal cross section, this is favourable for rotation.But the silicon-containing gas of leakage can deposit on reactor wall, especially deposit on the reactor wall of thermo-optical heating.
The air-flow with reactant gases (6) will be exposed to by the reactor wall (2) that heats and silicon is deposited by CVD.Most of silicon is in the localities the warmmest by being deposited on wall, namely near the region of heating unit.Therefore, settling forms the wreath (10) identical with helix structure heating installation by the inner side of cylindrical wall.This wreath (10) will contribute to keeping air-flow to rotate in reactor.When spiral thickness of deposits increases, the temperature difference of silicon wall (2) is by equalization, and therefore deposition will more uniformly occur on whole reactor wall (1).When pipe growth is closely and until when being all filled with pure silicon in the middle of reactor, as long as or to carry out on following process economy rationally, whole reactor is removed and is changed by new pasc reaction device.The wall thickness increased will cause the ever-reduced volume for silicon-containing gas (6), and production per hour will decline in time, and stop completely when pipe gets clogged.Heating unit (3) is preferably positioned at the incandescence of reactor outside, and incandescence transfers heat to the outside surface of reactor by radiation or contact heat.As the aforementioned, incandescence be shaped as around reactor wreath or be shaped as the heating unit of multiple inclination, the heating unit of inclination forms wreath around reactor or helix structure together.In addition, heating installation can be divided into several sections over each other, can control separately the temperature of each height of reactor.Heat is directed across the inner side (2) of silicon wall (1) to wall from incandescence (3), and the inner side of wall will form surface the hottest in reactor, and deposition advantageously occurs on the hottest surface.
With reference to figure 4, reactor is closed or almost closed cylindrical or Polygons (limit, three limits or more) container, has wall (1), top board (7) and base plate (4).Polygonal container is assembled by flat plate.Container is preferably made up of non-polluting material, is preferably made up of the silicon of enough purity, and whole reactor can be further used in production substantially.Therefore, in batchwise process, reactor intention is only only used once.Reactor by heating installation (3) that is complete or that be divided into several sections around.Heating unit can be fixing rod type element possibly.The reactant gases (6) be supplied to by base plate (4) is silicon-containing gas, preferred SiH 4or there is the gas of silica flour, be in most of the cases the silicon-containing gas with H2 gas and vapor permeation.The base plate (4) of reactor comprises one or more penetrating straight aperture (17), and hole (17) are as the nozzle of reactant gases (6).Hole (17) can be arranged in the mode of infinite number and can be shaping in a number of different ways, and this depends on desired flow pattern.Hole (17) between its center and cylindrical wall can be gear to actual circumstances, and making inwardly to grow stylish nozzle at wall can come into operation.Top board (7) also comprises hole (8), and to make residual gas (9) can dissipation, residual gas (9) be resistates from reactant gases (6) and forms primarily of H2 in almost desirable process.Hole (8) in top board (7) is disposed in center in the following manner: make poor silicon residual gas (9) can dissipation, and remaining reactant gases (6) can stop in the reactor, until silicon as much as possible is released.If hole (8) are tubulose and slightly extend downwardly in reactor, can be also favourable.This can produce whirlwind effect, and whirlwind effect can further improve the utilization ratio of reactant gases.
Advantageously to produce the iptimum speed of parallel streamline or flow pattern, be there is by hole (17) supply in base plate (4) air-flow of reactant gases (6).Reactant gases (6) is entered reactor by base plate (4) and is moved upwardly through reactor.By making whole reactor rotate (16), reactant gases (6) will be exposed to centripetal acceleration, and centripetal acceleration forces the wall of gas (6) orientating reaction device.Silicon-containing gas is obviously heavy than residual gas (9), therefore will be exposed to larger power.This make silicon-containing gas (6) be forced near it deposits silicon by the wall (2) heated, and residual gas (9) has to give way and motion closer to the center of reactor.Reactant gases (9) will eventually through hole (8) dissipation in top board (7).Reactor can be vertical, that tilt possibly or has entrance at top and have outlet in bottom.Because the part of whole reactor or reactor rotates (16) with enough speed of rotation, reactant gases (6) is exposed to centripetal force.This can be implemented, because electric motor (not shown in FIG.) makes reactor rotate (16).Usually revolving reaction wall (1) is only needed, if but base plate and top board (4 and 7) also rotate (16) is favourable, to realize possible optimal flow pattern.If due to structural factor, more advantageously make to rotate with reactor around the heating unit (3) of reactor, metering facility (not shown in FIG.), insulating part (not shown in FIG.) and other elements, this is feasible.Gas enters (6) and leave (9) needs to be advanced through the special unitor (18) allowing to rotate, such as rotating unitor.Most of electron device and metering facility (not shown in FIG.) can be advantageously wireless.
Reactant gases (6) will obtain the rotation identical with reactor, and therefore will without tangential velocity component relative to reactor wall (2), only has along reactor wall (2) little velocity component upwards.Relative rate little between this wall (2) causing reactant gases (6) and reactant gases to be deposited thereon, in order to avoid the formation of particle or fine powder, this is favourable.The centripetal force produced owing to rotating (16) will force reactant gases (6) outwards orientating reaction wall (1).Gas is by separated, because the heaviest molecule is exposed to maximum power, therefore, the heaviest molecule will be positioned near wall.Light molecule is given way having in heavier molecule, and is therefore positioned closer to rotation.When this concrete, this is especially favourable because siliceous reactant gases (6) is obviously heavy than residual gas (9), the release from residual gas (9) of most of silicon.Therefore, make heavy reactant gases (6) near wall by being formed, and make the gradient at light residual gas (9) the inwardly center of reactor.Because reaction surface (2) will be provided quickly the fact of new reactant gases, this produces higher sedimentation rate.Most probable is also improved gas effciency by this, reduces the silicon concentration in waste gas.
In polygonal container, base plate additionally can be equipped with upright opening (15), and upright opening (15) is positioned at the every nook and cranny place in the transitional region between two sidewalls.When starting reactor by uprush supply passing hole (15) for some time of reactant gases will be had, silicon can fast deposition between the sidewalls, therefore almost sealed reactor.This can realize before reactor starts to rotate.Realize the leakage limiting silicon-containing gas early thus, cause sealing connection gradually because reveal, make polygonal container obtain more circular internal cross section.
Have reactant gases (6) air-flow will be exposed to heat reactor wall (2) and silicon will be deposited by chemical vapour deposition (CVD).More silicon will be deposited on the hottest place of wall, therefore, can control deposition to make settling equally distributed mode in whole reactor.When pipe growth is closely and until when the centre of reactor is all filled with pure silicon, as long as or to carry out on following process economy rationally, whole reactor is removed and is changed by new pasc reaction device.The wall thickness increased will cause the ever-reduced volume for silicon-containing gas (6), and production per hour will decline in time, and stop completely when pipe gets clogged.
When reactor is so full, so that when reactor is unfavorable for continuing operation process, stop gas injection, rotation and heat supply.In the mode making CVD technique to restart, reactor is removed from the container with heating unit (3), and inserts the reactor of new sky.Therefore, this technique is not successive processes but batchwise process, but, quickly can change so that realize the highest possible turnout.The reactor being filled with silicon can be directly for further processing, such as, enter in smelting furnace.When using the another kind of material of non-silicon in reactor wall (1), base plate (4) and/or top board (7), before reactor can be used to processing further, this material require is removed, such as, do not removed by mechanical workout.The outside dimension of reactor can be suitable for further processing.
Heating unit (3) is preferably positioned at the incandescence of reactor outside, and incandescence transfers heat to the outside surface of reactor by radiation or contact heat.Heating installation can be divided into several sections over each other, can control separately the temperature of each height of reactor.Heat is directed across the inner side (2) of silicon wall (1) to wall from incandescence (3), and the inner side of wall will form surface the hottest in reactor, and deposition advantageously occurs on the hottest surface.Incandescence also can be arranged on base plate or top board, and incandescence is protected, because incandescence is arranged in rare gas element/cooling gas inlet coaxially, this is particularly advantageous and Energy Efficient, because directly heat on the surface that siliceous deposits occurs.
Reactor of the present invention and method be included in described herein, mention or the feature in any operative combination set forth and/or step, this combination is the embodiment of reactor of the present invention and method respectively.

Claims (14)

1., for the reactor by chemical vapour deposition CVD production solid silicon, described reactor comprises:
Reactor volume part;
Rotating equipment, described rotating equipment is operationally arranged into described reactor, rotates about the axis for making described reactor enclose during by CVD production solid silicon;
At least one is for the entrance of Silicon-rich reactant gases, and described entrance is arranged in the top of described reactor, bottom or end;
At least one is for the outlet of poor silicon gas, and described outlet is arranged in the top of described reactor, bottom or end;
At least one sidewall, at least one side wall ring described is around described reactor volume part; And
Heating installation, described heating installation is operationally arranged to heat described sidewall;
Wherein when described reactor rotates, the CVD of solid silicon occurs in by the internal surface of described sidewall that heats, and described rotation is provided in the heavier gathering of Silicon-rich reactant gases on described sidewall of the swirling eddy in described reactor volume part and the deposition for solid silicon.
2. reactor according to claim 1, is characterized in that, described reactor volume part is made up of silicon or is had the internal surface at least partially that inner silica layer makes silicon face be formed to be close to described reactor volume part.
3. reactor according to claim 1, it is characterized in that, described reactor comprises the profile of the cylinder form with circle or substantial circular cross section, described right cylinder is positioned vertically, described sidewall is made up of Metallurgical Quality or purer silicon, and one or more described entrance is arranged in described bottom, and described outlet is arranged on the top of described reactor.
4. the reactor according to any one of claim 1-3, is characterized in that, described reactor comprises or is operationally arranged into the described heating installation in described reactor outside.
5. reactor according to claim 1, it is characterized in that, described reactor comprises the profile of the cylinder form with circular interior cross-section, be operably connected to described reactor to rotate the electric motor of described reactor, the described outlet for poor silicon gas coaxially arranged with described cylinder axis at least one end, at least one is for the described entrance of Silicon-rich reactant gases, operationally be arranged in heating installation described at least one in the outside or inside of described reactor, described heating installation tool is with or without rare gas element and/or cooling gas protection.
6. reactor according to claim 5, it is characterized in that, described electric motor is operably connected to described reactor to rotate described reactor, described reactor comprises at least one end plate rotated with described reactor, described end plate is equipped with at least one described entrance for siliceous reactant gases, and described end plate is made up of the material with the thermal conductivity lower than the thermal conductivity of the rest part of described reactor, to avoid in described ingress deposition and to make thermosteresis minimum.
7. reactor according to claim 6, is characterized in that, described end plate is made up of the composite structure of the material of different thermal conductivity.
8. reactor according to claim 1, is characterized in that, the wall of described reactor is made up of any material standing operational condition.
9. reactor according to claim 1, is characterized in that, the wall of described reactor is made up of the low stain material standing operational condition.
10. reactor according to claim 1, is characterized in that, the wall of described reactor is made by standing the quartz of operational condition, silicon nitride or graphite.
11. 1 kinds of methods of producing solid silicon, described method is undertaken by vapour deposition and/or clean silicon-containing gas in reactor according to claim 1, said method comprising the steps of:
During production solid silicon, make described reactor enclose rotate about the axis;
Heating ring is around at least one sidewall of reactor volume part;
By entrance, reactant gases is introduced in described reactor; And
When described reactor rotates by the chemical vapour deposition of solid silicon by production solid silicon on the internal surface of described sidewall that heats,
Wherein said rotation is provided in the heavier gathering of Silicon-rich reactant gases on described sidewall of the swirling eddy in described reactor volume part and the deposition for solid silicon.
12. methods according to claim 11, it is characterized in that, mode is closely grown to make the cross section of described reactor, deposited wittingly on the reactor wall by silicon by chemical vapour deposition, therefore the contents of described reactor or the contents of described reactor and described reactor wall were used in for the production of the other stage in the technique of the silicon of electron device object.
13. methods according to claim 11, it is characterized in that, mode is closely grown to make the cross section of described reactor, deposited wittingly on the reactor wall by silicon by chemical vapour deposition, therefore the contents of described reactor or the contents of described reactor and described reactor wall were used in for the production of the other stage in the technique of the silicon of solar cell object.
14. reactors as claimed in one of claims 1-7 are for the production of silicon and/or the purposes cleaning siliceous reactant gases, described siliceous reactant gases is supplied from the CVD reactor of other reactors or other types, or described gas is originated from other, wherein when described reactor rotates, the CVD of solid silicon occurs in by the internal surface of described sidewall that heats.
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